Catalytic Oxidation of Benzene to Maleic Anhydride In a Continuous Stirred Tank Reactor

T . Q . PHUNG QUACH, D . ROULEAU, C . CHAVARZE and C . LAGUERZE*

Department of Chemical Engineering, Ecole Polytechniquc, Montrtal, Q d b e c
The kinetics of the vapor phase Oxidation of benzene has been studied over an industrial catalyst in a continuous stirred tank reactor in the temperature range from 280 to 430C and at atmospheric pressure. The products obtained are maleic anhydride, carbon oxides and water. The rate of the overall reaction (disappearance of benzene) is represented by the following expression based upon a steady state adsorption model

On a ktudiC la cinktique de l'oxydation du benzene en phase gazeuse et sur un catalyseur industriel; cette oxydation s'est faite dans un rkacteur h cuve soumis ?I une agitation continue, sous la pression atmosphkrique et ?I une Cchelle de tempkratures variant entre 280 et 430C. Les produits qu'on a obtenus sont l'anhydride malkique, les orydes de carbone et l'eau. LA vitesse de la rhctian globale (impliquant la disparition du benzhe) est reprksentke par l'expression suivante, laquelle est bade sur un modele d'adsorption en rCgimc stable:
rB =

The rate of formation of maleic anhydride is correlated by the equation

kskopepot koP?, -k 4kaPe

On a ktabli une corrklation relative au taux de formation de I'anhydride malkique au moyen de 1'6quation suivante:

which allows for a homogeneous depletion of maleic anhydride. , kZcg1 were found to follow Arrhenius The rate constants k,, k behavior
In kB
=

__

13.40

24 576.

RT
64 280. RT
-~

dans laquelle on prkoit un appauvrissement homogene de I'anhydride malkique. On a constat6 que les constantes de vitesse kn, k , et ktCg) suivaient le comportement d'ArrhCnius:
Ink*= 13.40 - _ 24,576 __ __

In ko

67.83
~

R
3.43

RT

In k2(")

__ -

33 427.

RT

67.83 64,280 lnko= _ _ -_ __

RT

he vapor phase oxidation of benzene has gained considerable importance in the past a s a commercia1 method for producing maleic anhydride. Its importance in the production of different type of alkyl resins, of maleinized drying oils and of various copolymers is well known. It is also used in the manufacture of organic pigment rubber, pharmaceutical products and detergent. The catalytic vapor phase oxidation of bezene has been the subject of a number of kinetic studies. This complex reaction may consist of several successive and parallel steps yielding a number of products such as phenol"je', h y d r ~ q u i n o n e ' ~ ~formaldehyde ~', and diphenyl"'. The overall rate of oxidation of benzene has been interpreted by a variety of kinetic models. The two models most frequently mentioned are the steady state oxidation-reduction model proposed by Mars and Van Kre~elen'~', and the steady state adsorption model proposed by Sheldstad, Downie and Graydon"'. Mars and Van Kre~elen'~' assumed that benzene from the bulk stream reacts with oxygen on the catalyst surface and the partly reduced surface
"Inetitnt du Genie ChirniQue. Toulouse, France.

3.43 In k z ( 0 )= __ R

___

33,427

RT

of the catalyst is reoxidized by oxygen from the bulk stream, while in the steady state adsorption model"' the reaction is assumed to take place between adsorbed oxygen on the catalyst surface and the reactant molecule in the gas phase. In fact, both yield the same mathematical rate equation. The Langmuir-Hinshelwood and Rideal mechanisms together with the power law type rate equations have also been used to evaluate and describe much of the experimental heterogeneous catalytic data in the literature. The objective of this work is to derive a model for the rate of disappearance of benzene and the rate of formation of maleic anhydride from the oxidation of benzene over a typical readily available industrial catalyst. A continuous stirred tank reactor which is an ideal reactor for determining the kinetics of heterogeneous reaction"' was used.

Experimental
Apparatus Figure 1 shows schematically the apparatus used

72

The Canadian Iournal of Chemical Engineering, Vol. 56, February, 1978

Rate Equation
TB =

Temperature

Parameter Estimation
k
a
= =
=

Residual Mean
0.4263

squares

Pi 1

280

b
330

0.000702 0.27 0.27 0.004439 0.53 0.21 0.010135 0.23 0.023423 0.62 0.29 0.0001977 0.1852 -0.0096 0.0004387 0.1137 0.3168 0.3991 0.2330 0.2261 0.0039612 -0.1451 0.2746 0.4582

10-9

k
u

= = = = = = = =

0.1056

x
x

10-7

380

k
a

d
Figure 1 -Flow diagram of apparatus A rotameters; B saturator; C constant temperature bath; D temperature controller and indicator; E reactor; F catalyst basket; G vaporizer; I magnetic stirrer; J ice trap; K moisture trap; L gas sampling valve; M SF 96 column; N Porapak R column and molecular sieve column; P chromatograph; Q condensers; R manometers; S pressure regulator.

= 0.62

0.1598

10-7

430

k
a

b
280
a'

0.9064

10-7

kM =

= 0.1183
= = = = =

0.2800

b'

x 10-9

m
330
k,u

a' = 0.5252

0.3171

b'

10-9

in this investigation. The construction of the reactor was described p r e v i o ~ s l y ' ~ - ~ Air ~ ' . was fed to the system by a calibrated rotameter and benzene was introduced by passing nitrogen through a saturator placed in a constant temperature bath. The line between the saturator and the reactor was electrically heated to avoid partial condensation of the benzene vapor in the gas stream. Benzene and a i r were mixed before entering the reactor. The products from t h e reactor were analysed by chromatography.

m
380
a'

b' m
430
knr
a'

= = = = = = =

0.6585

x lo-*

0.3444 X lo-'

b'

Catalyst
The catalyst V,OS on silica in the form of granules about 4 mm in diameter was obtained from t h e Catalyst Development Corporation, Little Ferry, New Jersey, U.S.A., under the name of F B 203s.

Results
Various factors may effect the reaction rate data obtained from gas solid catalytic reaction such as homogeneous reaction, activity of the catalyst, heat and mass transfer resistances. The effects of these factors must be reduced to a level of insignificance in order to establish a mechanism which deals only with the chemical aspect of the reaction. In the absence of a catalyst, the oxidation of benzene could not be detected in this study a t 450C. The standard run to determine the activity of t h e catalyst was performed frequently and a t the end of each run, a i r was passed through the reactor to remove any organic material remaining inside the reactor. The effect of the external transport resistance was minimized in this study by maintaining the stirrer speed higher than 20 r/s, the value a t which the reactor rate ceased to depend on agitation. Moreover, at t h e above stirring speed and total flow rates (3 3 15 ml/s), the reactor can be considered to be completely mixed(l2). The temperature and concentration gradients were estimated to be negligible by calculating the heat and mass transfer coefficients"'? The effect of internal transport resistance was verified by crushing the catalyst into smaller particles. The rate of the reaction did not change when the same weight of catalyst was used. The rate of catalyst oxidation of benzene was studied at four temperatures: 280,330,380 and 430C. The mole percentage of benzene varied from 0.45 to 8.23% and oxygen from 2.21 to 20.40%. The total flow rate varied from 3 to 15 ml/s. All experiments were carried out a t atmospheric pressure. The conversion of benzene X , was defined as the mole per hour of benzene reacted over the mole per hour of

Analysis A Victoraen chromatograph with two detectors was used for the analysis of both reactants and products. A 2 m long and 6 mm diameter, stainless steel column, packed with 20% SF96 on acid chromosorb w, 60/80 mesh was used together with a flame ionization detector to analyse benzene and maleic anhydride. For the analysis of oxygen, nitrogen, carbon dioxide, carbon monoxide, a thermal conductivity detector and two columns in parallel, porapak R and molecular sieve 5A, were used. All the columns operated at 140C.
Procedure

A known weight of catalyst was charged to the reactor. The catalyst was activated by passing a i r through the reactor a t 500C f o r about 24 h. The compositions of reactant and product were found by chromatography. Fifteen minutes a r e allowed in order to attain thermal equilibrium and steady state condition. Five or more readings were taken f o r each run and an average value of the compositions was used for the calculation of reaction rates ; composition values seldom differed by more than 3%. A material balance on the feed and product streams showed t h a t no products other than maleic anhydride, carbon oxides and water could be present in any appreciable amount.

The Canadian journal of Chemical Engineering, VoZ. 56, February, 1978

73

TABLE 2 REACTION RATE

MODELS

Model

Assumptions

Rate equation

SSAM

+ reaction of maleic anhydride

SSAM

+ dissociation of oxygen + reaction of maleic anhydride

Hougen-Watson model : surface reaction between adsorbed benzene and adsorbed oxygen Hougen-Watson model : surface reaction between benzene in the gas phase and adsorbed oxygen

benzene fed. The selectivity to maleic anhydride S was defined as the mole per hour of maleic anhydride formed over the mole per hour of benzene reacted. The rate of disappearance of benzene and the rate of formation of maleic anhydride were calculated as :
TB

Rate equations of heterogeneous type

The models presented in Table 2 are based on the reaction of benzene and oxygen of the following stochiometry :
CeHa

( W,FB) . . . . . . . . . . . , . . . . . . . . . . . . .

.. . . . . .

'

. (1)

+ nO2 -+ products

kB

(5)

The mass of the catalyst W used in this work was 28.0561 g. Kinetic analysis for t h e rate of disappearance of benzene :

Rate equation of power l a c t g p e :

The rate of disappearance of benzene was f i r s t fitted to a power law type rate equation:
(3) The parameters in this equation, the rate coefficient k and the rate orders a and b were estimated by linear regression (Table 1 ) . The rate coefficient k obeys Arrhenius behavior
Ink=
75.57 rs = k p ; &

n is the number of moles of oxygen consumed per mole of benzene oxidized. Model 1 is the steady state adsorption model, developed by Downie et al('). The reaction is assumed to take place between adsorbed oxygen on the catalyst surface and benzene in the gas phase. Rate of adsorption of oxygen = koPo (1 - 13). Rate of removal of oxygen by chemical reaction = n x rate of oxidation of benzene = mkSPS6. At steady state, the rate of adsorption of oxygen is equal to the rate of removal of oxygen by chemical reaction or:
n koPRe
=

kOP0 (1 - 8 )

so the rate of oxidation of benzene is:

78 =

kRkoPBPo koPn nk&R

(model 1)

73 884 RT

(4)

The values of a and b from the power law rate equation show that the order with respect to benzene is not rigorously constant over t h e entire temperature range. This, together with the fact t h a t its value is less than 1, points toward a rate equation of the so-called heterogeneous type. Moreover, the present work clearly showed that the reaction rate of benzene i s not independent of the partial pressure of oxygen under the conditions employed. Therefore models of the type Hougen W a t ~ o n " ~ ~ and ' ~ ' Downie et alC6'f o r t h e overall oxidation of benzene are to he preferred.

Model 1, however turns out to be the same in mathematical form as that of Mars and Van Krevelen'''. The two constants in Mars and Van Krevelen's model are reaction rate constants, while for the steady state adsorption model, one is a reaction rate constant and the other a n adsorption constant f o r oxygen. Models 2, 3, 4 and 5 a r e the same a s model 1but with the additional assumption that in model 2, the adsorption of oxygen involves the interaction of a single surface site and an atom of oxygen; in model 3, the desorption rate of oxygen is not negligible; and in model 4,the reaction of maleic anhydride with oxygen occurs to a significant extent i.e. this reaction contributes to the disappearance of oxygen from the surface by chemical reaction. Model 5 is the same as model 4 except that oxygen is considered to be

74

The Canadian Journal of Chemical Engineering, Vol. 5 6 , February, 1978

TABLE 3
PARAMETER ESTIMATION

- ISOTHERMAL
Non-linear estimation

REGRESSION

Model

Temperature "C 280

Linear estimation
ka, = ,01630 ko = .00796 k B = ,03272 ko = .04180 k B = .05121 ko = .lo505 ka = .06702 ko = ,49063
kB =

Standard deviation .00285 .oO077 .00567 .00423 .00813 ,01278 .01025 .20461 .00419 .oO018 .00889 .00114 .00681 .00194 .00875 .01173

330 380 430

280

,01625 .00793 .03427 ,04134 = .05028 = .lo410 ks = .06583 ko = .45897

kr, ko ks ko ke ko
= = = =

I
I

Residual mean squares .6406

x .5316 x

10-9 10-8 10-7 10-7

330
2

ko = .00251

.02185

380 430

.03946 .01072 .05217 ko = .02336 k s = .07292 ko = .06002

kB = ko = ks =

ks ko ks ko ks ko ka ko

= =
=

= = = = =

.02188 ,00251 .04080 .01075 .05269 .02303 .07296 .05783

x .5562 x .4472 x .6651 x .7918 x .1808 x

.igx

10-8
10-8

10-7

dissociated upon adsorption. Models 6 and 7 are the familiar Hougen-Watson rate e q ~ a t i o n " ~ ~with ' ~ ' , the different assumptions on the adsorbed reactants. The criteria for model rejection were: 1. Unacceptable characteristics of the estimates of the parameters. Kinetic and adsorption constants must be positive. 2. Lack of f i t of the model to the data as shown by an excessively large residual mean square. (test

F).
3. The rate and adsorption constants should obey Arrhenius behavior. All the models in Table 3 were linearized with respect to the rate parameters and then fitted to each set of isothermal kinetic data. The resulting correlations and rate parameters obtained for the seven models were then examined in terms of the criteria given above. Of the seven models presented in Table 2, only models 1 and 2 satisfied all the three criteria. The other models, 3, 4, 5, 6 and 7 were rejected due to criteria 1 and 3. But the analysis by linear regression does not give sufficient criterion t o discriminate between the remaining two models. Therefore this procedure was followed by a non linear regression analysis, using the results of the linear analysis as preliminary estimates for the values of the parameters. The results from the non-linear regression analysis of the two models 1 and 2 (Table 3 ) were found to satisfy the criteria above. Therefore the two sate models 1 and 2 could not be rejected statistically after the isothermal regression. Blakemore and H0er1"~' pointed out that after the grossly inadequate models have been eliminated, the whole set of data should be treated simultaneously. Therefore nonisothermal regression and a goodness of f i t test were applied to the data for both models in order t o discriminate between them. The effect of temperature on the rate expression was introduced by substituting the Arrhenius temperature dependence relation for each of the constants.
ko = exp ( A S ; / R ) exp ( - A H g / R T ) ko
=

after three iterations. Table 4 shows that there is a significant lack of f i t a t the 95% confidence level for both of the non isothermal regression tested. Considering however that the repeated runs of this work have not been quite genuine repeats for non isothermal analysis due to the experimental procedure which originally did not plan for temperature changes between replicated runs, the pure error is in all probability much larger than the estimated value of 0.0165 x 10' for S.". Hence, it is reasonable to seek less stringent grounds for model rejection and by moving to the 99% confidence level the lack of f i t is no longer significant for model 2. From the statistical analysis of the data, i t was then concluded that: model 2

was the most probable model to represent the rate of the overall oxidation of benzene in the temperature range from 280 to 430C. The rate and adsorption constants ks and ko were expressed as a function of temperature as follows:

In ko

= __

67.83 - 64 280. RT R

......................

(9)

The value of n will be justified later. Kinetic analysis for t h e rate of formation of maleic anhydride The rate data was first fitted to a power law type rate equation :
rill = kMPsl PA' P . G . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. (10)

.
....

(6)

exp ( A S i / R )exp ( - AH;"/T)

. (7)

The preliminary estimates of AS and AH were obtained by first plotting the rate constants versus 1 / T . With these values, the non linear program converged

The values of a', b', rn, from the power law rate equation show that the order with respect to benzene, oxygen and maleic anhydride are not constant and the values of a' and m change sign with respect to temperature (Table 1). Therefore the power law model can not be chosen to represent the rate of formation

The Canadian journal of Chemical Engineering, Vol. 56, February, 1978

75

TABLE 4
ANALYSIS OF VARIANCE

(Non isothermal study)

I
I I

Model

Source Residual Lack of fit Pure error Residual Lack of fit

square
1.0468 x 1.0369 x 0.0099

Degree of freedom
52 46

Mean of square
0.2254 X lo-' 0.0165 X 10-7 0.1033 x 10-7

F=
13.66

x 0.4851 x 0.4752 x

10-6

6 52

10-6

pure error

6.26

F (46, 6, 0.95) = 3.76 F (46, 6, 0.99) = 7.12

of maleic anhydride. The most general reaction scheme for the oxidation of benzene can be written as
benzene
k3

duces to:

+ ,

,
' +

0 2

maleic anhydride 1 k? carbon oxides

kl
4

+ carbon + water
oxides

(11)

The selectivity is defined a s :

(16)

water

-+

If the oxidation of maleic anhydride contributes to the disappearance of oxygen from the surface by chemical reaction, then the rate o f removal of oxygen by chemical reaction will be: (alkl a s k s ) Pd3 &a k2 P y O where al, a2, a3 a r e the stoichiometric numbers for the reaction sequence 11.

The rate of adsorption of oxygen is: koPp (1 (oxygen dissociated) At steady state : 8 =
k&< koP2

e)

+
+

(aikl

a3k3)

PB

+ azkz

P.hi

- for the overall rate of disappearance of benzene:

TB

The rate equations can be expressed as:

(ki

From Equation (16) it is obvious t h a t the selectivity should remain constant at any given temperature. However, the experimental results indicate conclusively that this condition is not satisfied and hence that Equation (15) does not describe adequately the rate of formation of maleic anhydride. Further experiments were carried out in which a mixture of maleic anhydride and air was fed to the reactor. It was observed that even in the absence of the catalyst, maleic anhydride reacted with oxygen in the gas phase to form carbon oxides and water. The presence of the catalyst did not change the results appreciably (less than 15%). Furthermore, since the selectivity is high, approaching a t times 100% the problem can be reduced t o the classical case of consecutive reactions :
CbH6

+ ka) ko P S - ' ~
+ CY&~)
=
=

koPh'

(aiki

PB

+ ~~ikaP.tr

. . . . . . . . (12)

+ 402(,,,)

ka
---*

C4Kzos

+ CO + coz + HzO

(17)

Note that Equation (12) is the same as model 5 in Table 3 with:

kn

C4H203

+ EOA(a) k 2 ( d
)

2CO

+ 2 CO2 + HzO

(18)

kz alkl
a2k2

k3

kg

+ asks

n'k.1,

The stoichiometry of the above reaction sequence follows from the fact that the ratio of carbon monoxide to carbon dioxide was observed to be nearly equal to one. The rate of disappearance of benzene reduces to:
model 2

- for the rate of formation of maleic anhydride:

T Y =

koP2

(klPtl - kzPzr) koP? -. . . . . . . (13) (aiki (~3k3P ) B azkzP.v

and the rate of formation of maleic anhydride becomes :

From the regression analysis, the values of k z f r o m Equations (12) and (13) are not positive a t all four temperatures. If the oxidation of maleic anhydride with adsorbed oxygen is negligible, then the rate of disappearance of benzene becomes :

The values of k2(g) are presented in Table 5 and the constant was expressed as a function of temperature a s follows :
In
k2(y)

and the rate of formation of maleic anhydride re-

3.41 R

33 427. RT

. (20)

76

The Canndinn lournnl of Chemical Engineering, Vol. 5 6 , Pehruary, 1978

TABLE 5
VALUES OF

ka(g) FROM EQUATION (19)

Temperature
280 330 380 430

kz (g)
0.001189 0.001951

0.002032.
0.006859

The value of the exponent which gave the best f i t was: m = 0.5

Discussion
The results of this work show that the industrial catalyst used possesses a very good selectivity f o r the catalytic vapor phase oxidation of benzene to maleic anhydride. The total conversion of benzene increases continuously with temperature from 280C to 430C. While the selectivity for maleic anhydride increases initially with temperature up to 380C and then decreases: this has been attributed to the homogeneous thermal decomposition and oxidation of maleic anhydride a t high temperature. The results of Dmuchovsky et al"" showed that the selectivity t o maleic anhydride by the oxidation of benzene on a vanadia molybdena catalyst increases a s the temperature increases but the maximum temperature used was 377C; the maximum selectivity found at that temperature was around 65% for a residence time of 0.98 s. Germain et al(I7) obtained a selectivity t o maleic anhydride of about 70% which did not change appreciably with temperature and partial pressure. Ahmad et a1("' obtained a higher selectivity to maleic anhydride as the temperature increased on a Cr-V-Si catalyst but with a V-Mo-Si catalyst, the selectivity to maleic anhydride reached a maximum over the temperature range of 350 to 500C. Badarinayana et aI(''' used different catalysts for the oxidation of benzene and they found that the selectivity to maleic anhydride also had a maximum with temperature with a V205-Moos catalyst. Many workers(1s~,20,21) suggested that the oxidation of benzene could be described adequately by two reactions, one leading to complete oxidation and the other to maleic anhydride which is then further oxidized. The exact kinetics would depend on the reaction conditions. Under our experimental conditions, it seems that most of the benzene oxidized goes directly to maleic anhydride which is then decomposed or oxidized to carbon oxides. The model chosen to represent the data in this work, model 2, appears to be gathering support either directly or in a slightly modified form. Many a 1 t hers c I7.2Q3.24) selected model 1 (oxygen is not dissocinted on the cataIyst surface) to represent the rate of disappearance of benzene. In our study, model 1 also correlated the data satisfactorily but was nevertheless rejected due to a lack of f i t a t 99% level after the non-isothermal regression. Furthermore Vrbaski and Mathews'"' found t h a t the dissociative adsorption of oxygen should be taken into account. In their study, Ioffe and Lyubarksii'"' observed that a t low oxygen concentrations, the rate of disappearance of benzene was inhibited by maleic anhydride and was second order with respect to oxygen, Although our data were obtained a t low oxygen concentration, maleic anhydride was found to have no

influence on the rate. Moreover, Juusola, Mann and Downie'"' concluded t h a t t h e work of Ioffe and Lynbarskii'"), appeared to have internal inconsistency. No data for the rate of formation of maleic anhydride were presented in the literature from which the kinetics of the reaction could be determined. Trifiro et al(27'studied the oxidation of Butene t o maleic anhydride on a n M M o 0 4 based catalyst in a stirred tank reactor. They observed that the rate of production of maleic anhydride is about f i r s t order with respect to oxygen. The rate of decomposition of maleic anhydride was shown to be first order with respect to its concentration, no dependence on oxygen was found'"'. But StegercZ0' found t h a t the rate of oxidation of maleic anhydride was half order with respect to maleic anhydride and independent of t h e partial pressure of oxygen. This is in agreement with our proposed model. Hammar'20' also reported an increase in activation energy for the oxidation of maleic anhydride a t temperatures above 375C. This increase in activation energy may correspond to the pyrolysis of maleic anhydride in addition to the oxidation reaction. Finally it is of interest to note that the average amount of oxygen consumed per mole of benzene reacted was found to be equal to 4.76 from the experimental data. From the stoichiometry given by Equation (17), 4 moles of oxygen should be consumed per mole of benzene reacted. Since the average selectivity is equal to 65%, 35% of the maleic anhydride decomposes according to Equation (18). Hence the total amount of oxygen consumed should equal 4 0.35 x 2 = 4.70. This corresponds very well with the observed value of 4.76.

Conclusion
Of the standard catalysts available for the oxidation of benzene, the one selected in this study was chosen to favor the production of maleic anhydride. Various kinetic models have been tested on the overall reaction rate of benzene. The steady state adsorption model provides the best description of the data:

The rate of formation of maleic anhydride is also described by a steady state adsorption model as follows :

which allows for a homogeneous depletion of maleic anhydride. The rate constants K,, ko, krc,, obey Arrhenius behavior.

Acknowledgment
The authors wish to acknowledge the National Research Council of Canada for their financial support and the Programme de Coop6ration Franeo-QuBbBeoise No 01-04-10 for making possible the collaboration of the research staff of the Institut du Genie Chimisue de Toulouse. in the various phases of this research study.

Nomenclature
a, b
=

a', b',
FB

order with respect to benzene and oxygen in the rate of overall oxidation of benzene. order with respect to benzepe, oxygen and maleic anhydride in the rate of formation of maleic anhydride. flow rate of benzene, mol/h

The Canadian journal oj Chemical Engineering, Vol. 56, February, 1978

77

= rate constant in a power law type rate equation of

= =

=
=
=

=
=

= =

KB

KO
n n

=
=

= =
=

PB PA! R
7B 7M

Po

=
=

=
= =

S T
X
W

=
= = = = = = = = = =

the overall disappearance of benzene, mol/(g. h. atm(a+b)) rate constant for maleic anhydride formation, mol/(h.g. atm) rate constant for maleic anhydride decomDosition (with adsorbed oxygen), mol/(h.g. atm) rate constant for maleic anhydride oxidation (in the gas phase), mol/(h. g. atmo.5) rate constant for total combustion of benzene, mol/(h. g. atm), rate constant in power law type rate equation of the anhydride, mol/(g. h. atm (m+a+*)) reaction rate constant, mol/(g. h. atm) oxygen adsorption rate constant, mol/(g. h. atm) oxygen desorption rate constant, mol/(g. h. atm) reaction velocity constant combined with surface parameters in Hougen Watson models. adsorption equilibrium constant of benzene adsorption equilibrium constant of oxygen stoichiometric number mole oxygen required mole reacted benzene stoichiemetric number mole oxygen required mole maleic anhvdride oxidized partial pressure of benzene, atm partial pressure of oxygen, atm partial pressure of maleic anhydride, atm rate of disappearance of benzene, mol/(g. h) rate of formation of maleic anhydride, mol/(g. h) gas constant, J/(mol. K) selectivity Temperature, K conversion weight of catalysis, g activation energy of reaction, J/mol activation energy of oxygen adsorption, J/mol constant in Arrhenius equation for the reaction, (J/(mol. K) constant i n Arrhenius equation for the oxygen adsorption, J / (.mol. K). stoichiometric coefficient for the maleic anhydride formation stoichiometric coefficient for maleic :anhydride decomposition stoichiometric coefficient for total combustion of benzene. fraction of catalyst sites which are oxidized

References
(1) Newih, D. (198fi\ -- - - ,.
(2) Zalkind

(J. A p h Chem. U.S.S.R. 6, 681 1933). (3) Pigulevskii V. V. and Yamhemahya E Chem Abstr. 30, 1978, (1936). ( J : Gen. Chem. U.S.S.R. 5,16ib 193si. (4) S & Ckoyi,Abstr. 42. 6324 (leas) (J. SOC. Chem. Ind.

M. and Burpoyne, J . H.. Proc. R. SOC.A153. 448 Y . S. and Zolotarev 8.. Chem. Abstr. 28, 4039 (1934).

Ta!LFyi-

and Van Krevelen. D. W . . Chem. Enr. - - Sci. (Soecial .S U P ~ ~ 3. . ) 41 (1954). . (6) Shelstad. K. A., Downie, J . and Graydon. W. F.. Can. J. Chem. Eng. 38, 102 (1960). ( 7 ) Carberry. J. J., Ind. Eng. Chem. 56, 39 (1964). (8) ~hunE-Qu~$~l~~T. Q., and Rouleau, D., J . Appl. Chem. Bioteehnol.
(5) Mars.

--.----. P.

I.

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La, 440 [ I Y I b J .

k.

Mansueript received June 30, 1977 ; accepted for publication October

28. 1977.

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The Canadian Iournal of Chemical Engineering, V o l . 5 6 , February, 1978